Method for the catalytic dehydrogenation of hydrocarbons



Patented Mar. 6, 1945 METHOD FOR THE CATALYTIC DEHYDRO- GENATION OF HYDBOCARBONS KennethLK. Kearby, Elizabeth, N. 1., assignor to Standard OilDevelopment Company, a corporationoi Delaware OFFICE.

Application August 26, 1942, erial No. 456,266

Claims. (01. 260-669) This application contains a disclosure similar to that contained in the application of Kenneth K. Kearby filed February 14, 1942, and assigned Serial No. 430,873.

My present invention relates to catalytic dehydrogenation of hydrocarbons, and more particularly, it relates to improved catalysts for dehydrogenating oleflns and aralkyl hydrocarbons,

terial, iron oxide as an active ingredient, and a small amount of a. promoter which consists of an alkali or an alkaline earth oxide. In addition,

the catalyst may contain a small amount of a and to methods for preparingthe said catalysts.

My present invention is particularly adapted to the dehydrogenation of low molecular weight olefin hydrocarbons having from 2' to 10, preferably 2 to 6, carbon atoms, but is also applicable to dehydrogenation of aralkyl hydrocarbons, such as ethyl and propyl benzene to form styrene and phenyl, methyl ethylenes, and to convert isopropyl benzene to methyl styrene.

Recently, processes designed to convert butene to butadiene have become of increased importance due to the fact that-butadiene is an essential intermediate in one of the more important methods for the production of synthetic rubberlike materials.

In the production of diolefins from olefins by the catalytic dehydrogenation of mono-olefins, it is, of course. desirable to obtain as high a yield of the diolefin as possible per one passage of the butene through the dehydrogenation zone, and as a corollary to this purpose, it isalso a desideratum to this type of process to obtain assmall a an amount as possible of by -products. It is also desirable to conduct the dehydrogenation under such conditions that the foulingof'the catalyst is minimized to as great an extent as possible.

The efficiency of the catalyst is best measured in 3 terms'of per cent selectivity, which means the per cent of th total amount of initial material which undergoes conversion, which is converted to the desired product. For example, if 50% of the initial material undergoes conversion of some sort, and 30% of the initial material is converted to the desired product, then the per cent selectivity would be 60.

I have now discovered a new type of catalyst which when used under certain conditions in the dehydrogenation of hydrocarbons makes it possible to obtain substantially greater yields of the desired dehydrogenation product than can be obtained by the use of previously known catalysts. The nature of this new type of catalyst and the conditions under which it is used Will be fully understood from the following description.

- In the above referred to Kearby application, there is disclosed a dehydrogenation catalyst which comprises magnesium oxide as a base mastabilizer which stabilizer may consist of an oxide, of a metal of the right-hand side (transition series) of groups I, II, and III of the periodic system or certain non-acidic oxides.

As pointed out in the aforesaid prior Kearby application, the principal function of the prometer in these catalysts is to increase the dehydrogenating activity of the catalyst. The principal function of the stabilizer, when used, is to prevent the promoter from volatilizing or becoming inactive.

Now in my present application, I propose to use as a base, zinc oxide, and this material should constitute the major portion of the entire catalyst composition. The following table gives the range of each component which may be used:

Table Component 2232% Zn0.- F010: 3-50 Promoter" .5-15 Stabilizer 1-15 Among the alkali metal and alkaline earth oxides which may be used as promoters, are the oxides of calcium, sodium and strontium, but potassium oxide is greatly superior.

However, I wish to point out that some of the desired conversion is obtained by omitting the promoter and the stabilizer and compounding the catalyst only from the base and the active ingredients. The presence of silica gel amounting to 1% by weight of the total catalyst containing the four components mentioned above and silica,

REISSUED ter active constituents Table A:

is shown in the following Table A ilutene dehydrogenation at 2100' F., iced rate-800 volumes butane! vol. catalyst/ha; 7 vol. steam/vol. butane. Catalyst contains in parts by weight 802110; 58110; 5150,10 oxides listed below:

Active oxides Iss: Milo: C010: N150: C110:

Per cent conversion of mono 44 38 30 26 37 Per cent selectivity to butadione 60 75 04 83 One particularly effective catalyst of the above type' including the promoter and the stabilizer has the following composition:

Component 2:32

The above catalysts may conveniently be prepared as follows:

Example I A solution of 262 gram of MnSO4-4Hz0 and 77.2 grams of Cu(NO3)2-3H:O in 2 liters of H20 was stirred into a. suspension of 539 grams of zinc subcarbonate [2ZnCOs-3Zn(0H)z] in 2 liters of H20. A solution of 228 grams of KzCOs in 400 cc. of H20 was added and the solution heated for 1 hour at 80 90 C. The precipitate was filtered, thoroughly washed, and mixed with a solution of 37.5 grams of K2001 in 200 cc. of H20. It was dried, heated for 3 hours at 1200 F. and pilled.

The above catalysts possess a high degree of selectivity to the dehydrogenation of normal butone to butadiene, the selectivity being of the order of 70-85%.

In order to set forth rams Of copper the utility of my invention, the following description of tests in which butane-1 was dehydrogenated to form butadiene when employing a zinc oxide base catalyst is set forth below:

Example III A mixture of normal butenes (containing about 95% of butene 2) was passed for one hour at a rate of 800 volumes (normal temperature and pressure) per volume of catalyst per hour with 5600 volumes of steam at 1200" F. over the catalysts whose preparation was described above. Over the ZBOFB2OS CUO-K2O catalyst 44% of the butene was converted to other products with 69% selectivity (30.0% butene to butadiene) grams of ferric nitrate more although it is usually The amount of carbon deposited on the catalyst was about 2%. and 4.1% of the butcne was converted to oxides of carbon (mostly carbon dioxide).

Example IV Under similar conditions the ZnO-MnOz-CuO-KaO catalyst gave 38% conversion with selectivity (28.5% of the butene converted to butadiene). Only .3% of the butene was converted to carbon (deposited on the catalyst) and 4.3% was converted to oxides of carbon.

If the temperature is lowered or the feed rate is increased so that the total conversion is reduced to 25%, a selectivity of -85% may be obtained.

In carrying out the process using catalysts of the type above described, the hydrocarbon, preferably with steam, is passed over the catalysts at a rate between 50 and 5000, preferably between and 1000 volumes (measured at normal temperature and pressure) of hydrocarbon per volume of catalyst per hour. The ratio of steam to hydrocarbon is between 30:1 and 1:1, preferably from 8:1 to 4:1. The reaction chamber is maintained at a temperature between 1000 and 1600 F., preferably between 1100 and 1300 F. and under atmospheric, below atmospheric or above atmospheric pressure. The hydrocarbon which passes through the reaction zone unaffected may of course be recycled thereto.

The principal function of the steam is to dilute the hydrocarbon and thus reduce the partial pressure thereof in the reaction zone. At the same time, however, the steam performs another useful function in that it reacts with coke which may be deposited on the catalyst to form carbon oxides and hydrogen. The elimination of at least a portion of the coke in this manner tends to prolong the time the catalyst can be used before it requires regeneration. Thus the reaction portion of a complete cycle of reaction and regeneration may be as long as 15, 25 or 50 hours or preferable in operation to run for periods of /2 hour to 10 hours and then regenerate.

Regeneration of the catalyst may be efiected by shutting ed the flow of hydrocarbon and passing steam, air, or a mixture of steam and air through the catalyst mass while it is maintained at a temperature between 1100 F. and 1300 F. Following substantially complete removal of coke from the catalyst in this manner, the flow of hydrocarbon and steam may be resumed.

My present invention may he carried out either in the stationary bed type of operation or a fluid catalyst type of operation. In the former, the catalyst is contained in a case or reactor, and the mixture of steam and hydrocarbon is simply forced through the material, preferably being discharged into the top, forced through the catalyst, and withdrawn from the bottom. The catalyst is preferably in the form of pellets, pills. granules, and the like. In the fluid catalyst type of operation, the catalyst is in the form of a powder having a particle size of from 100 to 400 mesh and is discharged into the reaction zone from a standpipe together with the hydrocarbon to be dehydrogenated, and steam, the catalyst and vapors entering preferably at a point at the bottom of the reactor and passing upwardly through a grid and forming within the reactor a dense phase suspension, that is to say, a suspension of catalyst in the gases of a concentration such that each cubic foot contains from 2 to 35 or more lbs. of catalyst. This dense phase may be.

to 8 to 10 ft./sec. Continuity of operation may be thus obtained and the catalyst may be withdrawn through a bottom draw-oil pipe regenerated, it necessary, and returned preferably substantially uncooled through the aforementioned standpipe to the reactor. The precise details, however, of operating the reactor do not form an important aspect of my present invention and any known reactor adapted to provide good contact between the solid and gas may be employed.

To recapitulate, my present invention relates to improvements of dehydrogenation catalysts, to the methods of preparing such catalysts, and is characterized briefly by the fact that I employ a zinc oxide base in addition to oxides of iron, manganese, cobalt or nickel and a small amount of a promoter and/or a stabilizer. An outstanding advantage of my invention is that I may carry out the dehydrogenation of a hydrocarbon in the presence of large quantities of steam without injurying the catalyst and thus I may greatly extend the life of catalysts since the presence of steam tends to retard the deposition of hydrocarbon contaminants upon the catalyst. Also, the presence of steam makes it possible'to supply the heat necessary for this highly endothermic reaction by the superheating of the said steam at least in substantial part and also makes it possible, particularly with the stationary bed type of operation, to control the contact time since dilution with steam of the entering reactant makes it possible to vary the reaction time virtually to any desired value regardless of how small that contact time interval may be.

What I claim is:

1. An improved method for the catalytic dehydrogenation or hydrocarbons selected from the class of mono-oleflns and aralkyls having at least two carbon atoms in the alkyl group which comprises contacting said hydrocarbon diluted with from 1 to 30 volumes oi steam per volume of hydrocarbon at temperatures between about 1000 F. and 1600 F. with a catalyst comprising a major portion of zinc oxide and a minor portion of an oxide selected from the class consisting of iron oxide, manganese oxide, cobalt oxide, nickel oxide and chromium oxide and a minor proportion of a promoter comprising potassium oxide.

2. Process set forth in claim 1 in which the hydrocarbon is ethyl benzene.

3. An improved process for the catalytic dehydrogenation of one or the class of hydrocarbons consisting of mono-olefins having not more than six carbon atoms and aralkyls, which comprises contacting said hydrocarbons with a dehydrogenation catalyst at dehydrogenation temperatures, the said catalyst comprising a major proportion of zinc oxide and a minor proportion of one of the class consisting of iron oxide, manganese oxide, chromium oxide, cobalt oxide and nickel oxide, and a small amount or potassium oxide employed as a promoter.

4. An improved method for the catalytic dehydrogenation of hydrocarbons selected from the class of mono-olefins and aralkyls having at least two carbon atoms in the alkyl group, which comprises contacting said hydrocarbons diluted with steam at temperatures in the range or from about 1000 F. to 1600 F. with a catalyst consisting essentially of per cent by weight of zinc oxide. 20 per cent by weight of ierric oxide, 5 per cent by weight copper oxide, and 5 per cent by weight potassium oxide. I

5. The method set forth in claim 1 in which th amount or potassium oxide is from 0.5 to 15 per cent by weight.

KENNETH K. KEARBY. 

